Uv absorbent,light stable compounds

ABSTRACT

CERTAIN BIS-METHYLENE MALONIC ACID DERIVATIVES ARE USEFUL AS IMPROVED UV ABSORBERS. THEY HAVE SLIGHT SELF-COLOR, EXHIBIT GOOD FASTNESS TO LIGHT AND HEAT. THEY ARE INCORPORATED INTO LIGHT SENSITIVE POLYMERS.

tus,. or. 260-473 United States Patent N 0 Drawing. Continuation-impart of application Ser. No.

565,725 July 18, 1966, now Patent No. 3,546,270. This 1 application Aug. 31, 1970, Ser. No. 68,473

Claims priority, application Switzerland, July 23, 1965,

The portion of the term of the patent subsequent to Dec. 15, 1987, has been disclaimed Int. 'Cl. C07c 69/76 R 6 Claims "ABSTRACT OF THE DISCLOSURE Certain bis-methylene malonic acid derivatives are use- ,ful as improved UV absorbers. They have slight self-color,

exhibit good fastness to light and heat. They are incorvpora tecl into lightsensitive polymers.

CROSS REFERENCE This is a continuation in part of copending application Ser. No. 565,725, filed July 18, 1966 and now US. Pat.

- I 1 DETAILED DISCLOSURE Aryl and Z COOAlkyl Z CN wherein-,Zrepresents hydrogen, an alkyl or aryl radical, absorb UV light. Of these compounds, the two representatives o'z-carbethoxy and a-cyano-fi-phenyl cinnamic acid nitrile= have proved successful in practice, particularly in nitrocellulose, as UV filters and UV absorbers. Most other representatives of this class of compounds have not achieved any practical importance either because of lack of fastness to light or insufficient light absorption.

In addition to light fastness and absorption, also the iastness to sublimation of a UV absorber is becoming or greater and greater importance. At the high temperatures to which the thermoplastic masses are exposed in the modern machines which are built for high output, a considerable amount of the previously known UV absorbers of the cinnamonitrile series sublimes out of the thermoplastic mass. This leads not only to a loss of UV absorber and a reduction of the light stability of the plastic itself but also, in some cases, to fouling of the apparatus, e.g. of the injection moulds, or to partial blocking of the spinnerets. These disadvantages can also have a disadvantageous effect on the appearance and even the rigidity of moulded plastics. The disturbances of the production process due to the volatility of UV absorbers incorporated into the mass are directly due to the amount of deposited sublimate; relatively high volatibility of the UV absorber thus means more frequently interruption of the production process, more frequent cleaning of the apparatus and removal of waste. 1

CN Aryl 3,824,273 Patented July 16, 1974 v I It has now been found that the disadvantages described COR CORI wherein the groupings R represent independently one of the following:

R: OR;, NHR N and -N R each of R and R represents a member selected from among unsubstituted alkyl of from 1 to 22 carbon atoms, oxaalkyl of from 3 to 21 carbon atoms, dioxaalkyl of from 5 to 23 carbon atoms, hydroxyalkyl of from 2 to 12 carbon atoms, hydroxyoxaalkyl of from 4 to 12 carbon atoms, alkenyl of from 3 to 18 carbon atoms, cycloalkyl of from 5 to 6 ring members and a total of at most 12 carbon atoms, benzyl, aryl-substituted alkyl of a total of from 8 to 24 carbon atoms wherein the aryl moiety is selected from among phenyl, alkyl-substituting phenyl and oxaalkyl-substituted phenyl, aryl-substituted monooxa-alkyl of a toal of from 9 to 24 carbon atoms wherein the aryl moiety is phenyl or alkyl-substituted phenyl, phenyl, alkyl-phenyl of from 7 to 20 carbon atoms, oxaalkyIl-phenyl of from 7 to 20 carbon atoms;

r 71 YTRTY .14

represents a saturated heteroc-yclic radical of from 5 to 7 ring members one of the ring members, not directly linked to the ntirogen atom, being selected from among --CH -O- or -S- and the remaining members being selected from among --CH and CH- (lower alkyl) and the total of carbon atoms in said heterocycle not exceeding 8,

each of Y and Y represents a. member selected from among O, NHCO, -NHSO and the latter three members being bound by their nitro gen atom to rings A and B, respectively, each of R and R representing phenyl, alkyl-phenyl of from 7 to 18 carbon atoms, oxa-alkyl-phenyl of from 7 to 18 carbon atoms, and hydrogen, and R being free from the atomic configurations -obo-, Nb-o-, N-b-s-, -o=o-ol l l l l O=C-N d l l R represents alkylene of from 2 to 12 carbon atoms,

monooxaalkylene of from 4 to 12 carbon atoms, monot-hia-alkylene of from 4 to 12 carbon atoms, dioxaalkylene of from 6 to 14 carbon atoms, dithia-alkylene of from 6 to 14 carbon atoms, cycloalkylene of from 4 to 12 carbon atoms, aralkylene consisting ofan alkylene chain of from 2 to 16 carbon atoms the C- chain of which is interrupted by phenylene, alkylphenyl- Iene of a total number of carbon atoms not exceeding 20, oxa-aralkylene consisting of an alkylene chain of from 3 to 17 carbon atoms interrupted by one oxygen atom and from one to two phenylene radicals,

any heteroatom of R being separated by at least two carbon atoms from the next adjacent hetero atoms in Y and Y and from any other hetero atom in R and the hetero atom of Y nearest R being separated from the hetero atom of Y nearest R by at least two carbon atoms; 4 l r from to 1 of the hydrogen atoms in each of the benzene rings A and B being replaced by one of the following: fluorine, chlorine, bromine, alkyl of from 1 to carbon atoms, lower alkoxy of from 1 to 8 carbon atoms;

when Y is --O-, n represents 1 or 2 and in all other cases n represents 2.

In the groups represented by R represents an optionally substituted alkyl group, preferably i (a) an unsubstituted alkyl group haying 1 to 22 C atoms such as the methyl, ethyl, propyl, butyl, isobutyl, octyl, 2-ethylhexyl, dodecyl or octadecyl group,

-(b) an oxaalkyl group having 3 to 21 C atoms, e.g. a monooxaalkyl group such as the Z-methoxyethyl, 2-butoxyethyl, Z-decyloxyethyl or 4-methoxybutyl group, or a dioxa-alkyl group having 5 to 23 C atoms such as the 2-(2-isopropoxyethoxy)-ethyl group or the 4-(4-methoxybutoxy)-butyl group;

(0) a hydroxyalkyl group having 2 to 12 C atoms, e.g. the Z-hydroxyethyl, 2- or 3-hydroxypropyl or 4-hydroxybutyl group,

(d) a hydroxyoxaalkyl group having 4 to 12 C atoms, e.g. a hydroxy mono-oxaalkyl group such as the 2-(2-hydroxyethoxy)-ethyl or -propyl group or a hydroxy-dioxaalkyl group having 6 to 14 C atoms such as the 2-[2-(2-hydroxyethoxy)-ethoxy]-ethylor -propyl group;

an optionally substituted alkenyl group, preferably an unsubstituted alkenyl group having 3 to 1 8 C atoms, e.g. the allyl, methyallyl, A -undecylenyl or A -octadecylenyl group;

'an optionally substituted cycloalkyl group, preefrably of at most 12 carbon atoms and 5 to 6 ring members, e.g. a hydrocarbon group having a 5-membered ring and, in all, 5 to 12 C atoms, such as the cyclopentyl or 2-methylcyclopentyl group, or a 6-membered ring with, in all, 6 to 12 C atoms such as the cyclohexyl or 4-butylcyclohexyl group;

an optionally substituted aralkyl group, preferably a hydrocarbon group having 7 to 19 C atoms, which group contains an optionally alkyl-substituted phenyl radical, e.g. the benzyl, aand fl-phenylethyl, o-methylbenzyl, p-methylbenzyl or p-octylbenzyl group;

an optionally substituted monooxa-(aralkyl) group preferably having 8 to 24 C atoms and comprising an optionally alkoxy-substituted phenyl-alkyl radical or alkyl-substituted phenoXy-alkyl radical, e.g. the p-methoxybenzyl, p-butoxybenzyl, 2-phenoxyethyl, 2-benzy1- oxyethyl or 2- (p-dodecylphenoxy)-ethyl group, or

an optionally substituted aryl group which is preferably carbocyclic imono-nuclear, preferably an aryl hydro- ;carbon group having 6 to 20 C atoms or a monooxa- I (alkylaryl) hydrocarbon group having 7 to 20 C atoms and particularly, a phenyl ring optionally substituted by alkyl or alkoxy groups, e.g. the phenyl, mor pmethylphenyl, ptert.butylphenyl, p-tert.octylphenyl, p-

tert.dodecylphenyl, the 0- or p-methoxyphenyl, 0- or p-ethoxyphenyl or the m-dodecyloxyphenyl group.

R has the same meaning as R preferably however, it

" represents an unsubstituted alkyl group having 1 to 22C atoms such as the methyl, ethyl, propyl, butyl,

isobutyl, octyl, Z-ethylhexyl, dodecyl or octadecyl group;

R represents an al'kylene group bound to the nitrogen preferably by 4 to 6 C atoms, e.g. a tetra-, pentaor hexa-methylene group; or a monooxaalkylene or mono- 4 thiaalkylene grouphaving preferably 4 to 8 C atonis, e.g. the groups OHzCHrO-CHzCHz, CH;(|3HOCH;CH,

which groups, together with the nitrogen atomQform a 5- to 7-membered saturated azaheterocycle. Also,-in general formula I and in the following formulae:

Y and Y each represent a bivalent radical ofthe formula -NHCO, NHSO or NHCOO which radical is attached to the ring- A or B by the nitrogen atom, preferably however each represents O-,

R and R each represent an optionally substituted aryl group, particularly an aryl hydrocarbon group having 6 to 18 C atoms and preferably an alkyl-substituted or alkoxy-substituted phenyl radical, e.g. the phenyl, p-methylphenyl, p-tert.butylphenyl or p-octylphenyl, pmethoxyphenyl or o-dodecyloxyphenyl group, and

R represents an alkylene group having preferably 2 to 12 C atoms, e.g. the 1,2-ethylene, 1,2-propylene, trimethylene, tetramethylene, pentamethylene, octamethylene, dodecamethylene, 2,2,S-trimethyl-hexamethylene or 2,5-diethylhexamethylene group; a monooxaalkylene or monothiaalkylene group having preferably 4 to 12 C atoms, e.g. the groups a cycloalkylene group having preferably 4 to 12 C atoms e.g. the groups an aralkylene group, preferably an aralkylene hydrocarbon group having 8 to 22 C atoms, e.g. the groups CH3 CH3 I CH3 CH3 a monooxaaralkylene group, chiefly a monooxaaralky1- ene hydrocarbon group having 9 to 21 C atoms, the aryl moiety of the aralkylene and monooxaaralkylene groups preferably being an optionally alkyl-substituted or alkoxy-substituted phenylene radical, e.g. the groups atoms, and oxygen atoms bound to R and linking it to the benzene rings A 'and'B being bound at saturated carbon atoms of R ;'and

. n represents 2 or, when Y isoxygen, also 1.

Preferably the compounds of the formula I together contain at most 82 C atoms; in all the groups R R R and R6. l i

.In the above nomenclature, an oxa-hydrocarbon or thia-hydrocarbon radical :is a hydrocarbon radical in which a non-terminal, CH -group, i.e. one in the middle of a, sequence of carbonjatoms, is replaced by an oxygen or sulfur atom. The groups I are given as examples.

The 1,4-phcnylene rings. A and B can be substituted by chemically inert and non-colouring substituents; preferably however, they are unsubstituted in the 2-, 3-, 5- and 6-positions or theyare substituted in any, but at most two, of'these positions by halogen, e.g. fluorine, chlorine or bromine, low alkyl groups, e.g. methyl, ethyl or butyl groups, or alkoxy groups having 1 to 8 C atoms, e.g. methoxy, ethoxy or octyloxy groups.

Thenew bis-methylene malonic acid derivatives can be produced by various methods, for example:

A. By condensation of 1 mol of dicarbonyl compound of formula II o= L i (11) with 2 mols of identical or different malonic acid derivatives of formulae III and IIIa' com 1 (III) known conditions for Knoevenagel condensa- R R R5 /COR R OC r. V CORI (IV) (Iva) wherein Y, and Y represent the hydroxyl or amine group,

with 1 mol of a bifunctional alkylating or acylating agent wherein Z, when Y or Y is HO, represents halogen,

preferably the chlorine, bromine or iodine atoms or the radical of a strong oxygen-acid, preferably the radical of a sulphur-oxygen-acid;e.g. the radical OSO ---OSO low-alkylor --0SO -aryl and, when Y or Y, are H N-, 2 represents the group COZ', .-SO Z or --OCOZ' wherein Z is halogen, preferably the chlorine atom. Suitable alkylating agents of formula V are thus bis-esters of diols of the formula HOR -OH which are derived from a hydrohalic acid or a strong oxygen acid. Suitable acylating agents are thusdicarboxylic acid halides; di-

carboxylic acid chlorides are particularly. suitable'and in which Y and Y have the same meanings as in Formulas IV and IVa, by means of the bifunctional alkylating or acylating agents of Formula V.

Naturally, these carbonyl compounds of Formula VI or V'Ia can also first be condensed with the malonic acid derivatives of Formula III as described above for method A, to form the methylene malonic acid derivatives of Formulas IV and IVa which can be further reacted according to method B.

Compounds falling under Formula I can be produced for instance, from the following products usable as starting compounds in the processes described above:

(1) Dicarbonyl compounds of Formula II: 4,4'-diformyl diphenyl ether, 3-chloro-4,4-diformyl diphenyl ether (both obtained from the corresponding tetrabromine compounds by saponification or from the chloromethyl compounds (Sommelet)), 1,4-bis-(4-formylphenoxy)-butane, 1,2-bis-(3-methyl-4-formylphenoxy)-ethane (both obtained according to Gattermann), 1,5-bis-(4-acetylphenoxy)-pentane (obtained by etherifying p-hydroxyaceto-phenone with 1,5-dibromobutane), 4,4'-diacetyl-diphenyl ether, 4,4'-dibutyryl-diphenyl ether, 4,4'-divaleroyldiphenyl ether, ,4,4-dipropionyl-diphenyl ether, 4,4'-dipivaloyl-diphenyl ether, 4,4'-dibenzoyl-diphenyl ether (obtained according to Friedel-Crafts) and 4,4-dibenzylcarbonyl-diphenyl ether.

(2) Malonic acid derivatives of Formula III:

(a) Esters of malonic acid falling under Formula III and which are of the formula COOR:

COOR:

in which latter formula R; has the meanings given below:

Num- Numbar R; ber R2 1 Methy1.

3 Propyl.

5 Isobutyl.

7 Dodeeyl.

-met oxye y Z-ethoxyethyl.

13 2-butoxyethyl. 2-dodecyloxyethyl.

15 4-methoxybutyl. Z-nonadeeyloxyethyl.

17 2-(2t-trlrzilethoxyethoxyr 2-(2t-Il1m1toxyeth xyy e e y 19 2(e2t-Ill:?1-propoxyethoxy)- 20 4-()t-11ethoxybutoxy)- u 21....-. 4-(18-methoxyoctadecyl- 22"-... z-hydroxyethyl. 23 2 gig-butyl. l

.... y oxypropy 3-hydroxypropyl.

29 2-[2-(2-hydroxyethoxy)- 30 2-[2-(10-hydroxydecyloxy)a ethoxyl-ethyl. ethoxyl-ethyl. 31 Allyl. ethxllyl. 3 A -undecylenyl. A -octadeeylenyl. 35 Cyclopentyl. Cyclchexyl. 37 3-methyleyclohexyl. 4-t.butylcyclohexyl. 39 n-Hexylcyelohexyl. 40 Benzyl. 41 l-phenylethyl. 42"...- Z-phenylethyL 43 2.phenyloctadeeyl 44 m-Methylbenzyl. 45 p-Methoxybenzyl. 46 p-Decyloxybenzyl.

m-Butoxybenzyl. 48.. o-Methylbenzyl. 49 p-Dodecylbenzyl. 50.. 2-(2phenylethoxy)-ethyl' 51 2-[4-(p-n-dodecy pheny 62 2-benzyloxyethyl.

butoxyl-ethyl. 2-phenoxypropy1. 54 p-Butyl. p-T.butylphenyl. 56.; p-Octylpheuyl. p-TetrxdecylphenyL 58 p-Methoxyphenyl. p-Butoxyphenyl. 60 p-Octoxyphenyl. 61 p-Tetradecyloxyphenyl'.

(4) Carbonyl compounds of Formulas VI and VIa:

Number Number 193.1-.. p-Hydroxybenzalde- 194. B-ehloro--hydroxybenzalhyde. dehyde. 1195. 3isopropyl-4-hydroxy- 196"". Z-methoxy-t-hydroxybenzbenzaldehyde. aldehyde.

197- 3-methoxy-4hydroxy- 198. 3,5-d1methyl benzaldebenzaldehyde. hyde. 199. 2-butoxy-4-hydroxybenzaldehyde (these aldehydes are ob tained by the Vilsmeier-Haack method). 200..- p'Aminobenzaldehyde. 201 Z-chor-g-hydroxybenza e y e. 202.-. 2'fiuoro-4-hydroxybenz- 203... 3-ehloro-4-hydroxybenzaide y e. aldehyde. 204". 3-fluoro-4-hydroxybenz 205.-. 2bromo4-hydroxybenzaldehyde. aldehyde. 206- 3'bromo-4-hydroxybenz- 207 2-methyl-4-hydroxybenzaldehyde. aldehyde. 208".-- 3-methyl-4-hydroxy- 209..-" 2-bntyl-4-hydroxybenzbenzaldehyde. aldehy e. 210"--- 3-pentyl-4-hydroxy- 211..." 2-methoxy-4 hydroxybenz benzaldehyde. aldehyde. 212 3-methoxy-4-hydroxy- 213-.- 2butoxy4-hydroxybenzbenzaldehyde. aldehyde. 214- 3-oetoxy-4-hydroxy- 215 p-Hydroxybenzophenone. benzaldehyde. I 216. p-Hydroxy-p--methyl- 217-.. p-Hydroxy-p -ethy1benzobenzophenone. phenone. I 218- p-Hydroxy-p--t-butyl- 219... p-Hydroxy-p -dodecylbenzophenone. benzophenone. 220 p-Hydroxy-p-methoxy- 22l p-HydroXy-o dodeoyloxybenzophenone. benzophenone. 222 p-Aminobenzophenone. 223..." 3biipmo-4-hydroxyacetop enone. 224- 4-hydroxy-4rethylbenzo- 225 3methyl-4-hydroxy-4- phenone. butoxybenzophenone. 226. p-Hydroxyacetophe- 227 p-Hydroxypropiophenone.

none. 228- p-Hydroxybutyrophe- 229..- p-Hydroxyvalerophenone.

none. 230 p-Aminoacetophenone. 231-.. p-liglyt droxyphenylbenzyle one. 232..... p-HydroxyphenyM- 233..- p-Aminophenylbenzylphenylbutylketone. ketone. 234.-- p-Hydroxyphenyl-p- 235 p-Hydroxyphenyl-p-domethylbenzylketone. decylbenzyl ketone.

(These ketones are obtained by Friedel-Crafts acylation of the corresponding phenols.)

(S) Monomethylene malonic acid derivatives of For- Naturally, esters, particularly low alkanol esters of bismethylene malonic derivatives, i.e. compounds of Formula I wherein R represents a lower alkyl radical, can be converted into other esters by transesterification or into amides by reaction with amines. For example, 1,4-bis-[4- (2,2-dicarboethoxyethenyl)-phenoxy]-butane can be converted by transesterification with octadecyl alcohol into 1,4bis-[4-(2,2 dicarbooctadecyloxyethenyl)-phenoxy] butane. In addition to the simple alkanols, also oxaalkanols are suitable for transesterification; examples are 4-methoxyoutanol, 2-dodecyloxyethanol or 2-(2-butoxyethoxy)- ethanol, or hydroxy alcohols such as ethylene glycol, diethylene glycol, butane-1,4-diol or tri-ethylene glycol.

The new UV absorbers of formula I are incorporated into the light sensitive, particularly polymeric, carriers for light filters in amounts of 0.01 to 30%. Among other factors, the amount of UV absorber to be incorporated de pends on the thickness of the light filters to be produced. For very thin films such as, e.g. lacquer coatings, amounts of 1 to 20% are preferred, for thick layers such as in polymethacrylate sheets, on the other hand amounts of 0.01 to 1% are preferred.

As carriers for the new bis-methylene malonic acid derivatives of formula I, principally organic polymers are mentioned; also thermoplastic polymers as well as curable synthetic resins (thermosetting polymers) can be used, indeed both fully synthetic polymers as well as natural polymers as well as their polymer-homologous chemical modification products. By fully synthetic polymers are meant chiefly pure addition and pure condensation polymers, also however condensation polymers cross linked by addition polymerisation. Theaddition polymers which can be used as carriers for the new UV absorbers can be arranged according to the following main types:

1. Homopolymers and copolymers of vinyland vinylidene monomers which are converted into the corresponding polymers by radical, ionic or metal-organic polymerisation initiators. Examples of such monomers, their polymers or copolymers which are suitable carriers are:

polymerisable ethylenic unsaturated halogen hydrocarbon compounds, particularly vinyl chloride, vinyl fluoride and vinylidene chloride, polymerisable hydrocarbons having a double bond capable of addition, particularly styrene, isobutylene, ethylene and propylene, including both the atactic and also the isotactic forms of polymers.

a,fl-unsaturated polymerisable carboxylic acids and functional derivatives thereof such as acrylic acid, methacrylic acid, acrylonitrile, alkyl esters-particularly low alkyl esters-and amides of acrylic and methacrylic acid, e.g. the methyl, ethyl and butyl esters of methacrylic and acrylic acid; polymcrisable acyl derivatives of ethylenic unsaturated alcohols and amines, particularly those of organic carboxylic acids, in which case acyl radicals of alkane and alkene carboxylic acids having up to 18 carbon atoms and acyl radicals of aromatic monocyclic carboxylic acids such as benzoic acids and phthalic acids, as well as acyl radicals of cyclic carbonic acid imides such as those of cyanuric acid can be used. Examples are allyl phthalate, polyallyl melamines, vinyl acetate, vinyl stearate, vinyl benzoate and vinyl maleate; polymerisable polyenes having conjugated double bonds such as butadiene, isoprene, chloroprcne, sorbic acid and esters thereof.

2. Homopolymers and copolymers of epoxides, particularly of bis-epoxides formed by curing with acid or basic catalysts. Examples of this class are the polymers of bisglycidyl ethers of geminal bis-(p-hydroxyphenyl)-alkancs and cycloalkanes.

3. Homoand co-polymers of lactams and lactones, particularly the polymers of e-caprolactam.

4. Homoand copolymers of aldehydes, particularly of formaldehyde and acetaldehyde such as polyoxymethylene and polyoxyethylene.

5. Reaction products of isocyanates with hydroxyl and/ or amino compounds, particularly those from dior polyisocyanates with divalent or polyvalent hydroxyl or amino compounds. The polyurethanes and polyureas formed by reaction of diisocyanates with polyesters and/ or polyethers containing hydroxyl groups are in this class.

The condensation polymers which are used as carriers for the new UV absorbers are, among others, particularly polyesters and polyamides. Linear thermoplastic polycondensates which are derived from dicarboxylic acids and organic dihydroxy derivatives or organic diamines on the one hand and hydroxyor amino-carboxylic acids on the others are mentioned in particular. Preferred linear polycondensates are the fibre-forming polymers of w,w'-dlcarboxylic acids and w,w-dihydroxy compounds or awdiamines, also of w-hydroxycarboxylic acids or of w-aminocarboxylic acids, in particular those polymers which are derived from aliphatic, cycloaliphatic and carbocyclic nonfused aromatic carboxylic acids.

The linear condensation products of the following components are specially suitable: adipic acid-hexarnethylenediamine, sebacic acid-hexamethylenediamine, terephthalic acid-ethylene glycol, terephthalic acid-1,4-dimethylol-cyclohexane, IO-aminodecane carboxylic acid (ll-aminoundecylic acid).

Cross-linked polycondensates as carriers are thermosetting and are formed in particular by condensation of aldehydes with polyvalent compounds which can be condensed. Formaldehyde condensates with phenols, ureas and melamines can be mentioned.

Condensation polymers cross-linked by subsequent addition polymerisation are mainly the polyester resins, i.e. copolymers of polyesters of unsaturated organic carboxylic acids containing double bonds capable of addition with polyvalent, particularly divalent, alcohols, (these polyesters optionally being modified with dicarboxylic acids not capable of addition) with vinyl or vinylidene monomers. Monomers are preferably polymerisable mixtures of styrene and/or methylmethacrylate with condensates of maleic acid, itaconic acid, citraconic acid with divalent alcohols, preferably the water addition products of ethylene oxide and propylene oxide such as ethylene glycol, propylene glycol and diethylene glycol and optionally other dicarboxylic acids of the aliphatic, alicyclic and monocyclic/ aromatic series or anhydrides thereof such as succinic acid anhydride, phthalic acid anhydride, tetrachlorophthalic acid anhydride, the anhydride of 1,2,3,4,7,7-hexachlorodicyclo[2,2,1]-hept-2-ene-5,6-dicarboxylic acid and/ or of adipic acid.

This monomer mixture of unsaturated polyesters and vinyl and/or vinylidene monomers (often termed liquid polyester resin) is cross-linked, in a preferred embodiment, by radical polymerisation initiators.

The natural polymers which can be used as carriers for the new UV absorbers are principally polysaccharides such as cellulose, or also rubber and proteins.

Synthetic polymers the side chains of which have been chemically modified are principally the reaction products of polyvinyl alcohols with aldehydes such as polyvinyl butyral, and the saponification products of polyvinyl esters. Natural polymers the side chains of which have been chemically modified which can be used as carriers for the new UV absorbers are mainly cellulose esters and ethers such as cellulose esters of acetic acid, propionic acid, benzoic acid, having on the average 1 to 3 acyl groups per glucose unit.

The polymers given in the above list, either alone or in admixture, are the carriers for the new UV absorbers in the compositions of matter obtained according to the invention. Particularly valuable compositions of matter contain, as carrier for the new UV absorbers, thermoplastic vinyl and vinylidene polymers, including polyolefines, cellulose esters and ethers, linear fibre-forming polyesters, polyamides and polyurethanes, polyester resins.

In addition to these polymeric carriers, natural and also synthetic, light-sensitive waxes, fats and oils as well as complex systems such as photographic material, emulsions, which contain light-sensitive solid substances, emulsions or dispersions of the polymers mentioned above can be used as carriers for the new UV absorbers. A UV absorbent emulsion of a solution of compounds of formula I in high boiling solvents such as dioctyl phthalate, dioctyl sebacate, or in the gelatine layer of photographic materials is given as an example.

The molecular weight of the polymers mentioned above is of secondary importance as long as it is within the limits necessary for the characteristic mechanical properties of the polymers. Depending on the polymer it can be from 1,000 to several millions. The new UV absorbers are incorporated into these polymers, for example-depending on the type of polymerby working in at least one of these compounds and, optionally, further additives such as plasticisers, antioxidants, other UV absorbers, heat stabilisers, pigments, by the usual technical methods, into the melt before or during molding, or by dissolving in the corresponding monomer before polymerisation, or by dissolving the polymer and the additives in solvents and subsequently evaporating the latter. The new bis-methylene malonic acid derivatives can also be drawn from baths, e.g. from aqueous dispersions, onto thinner carrier structures such as films or threads.

The incorporation of the UV absorbers according to the invention into the monomer mixture of condensation polymers which split off water during the condensation at temperatures above 200 C. is to be avoided. The incorporation of the UV absorbers according to the invention into almost neutral carriers is most advantageous.

The light sensitive materials can also be protected from the injurious effect of light by giving them a protective coating containing at least one compound of formula I as defined or by covering them, for example, with films, discs or plates containing such UV absorbers. In both these cases, the amount of UV absorber added is advantageously 10 to 30% (calculated on the protective material) for protective coatings of less than 0.01 mm. thickness and 1 to 10% for protective coatings of 0.01 to 0.1 mm. thickness.

For certain purposes, particularly when warm polymers in the form of chips have to be pulverised together with protective substances, UV absorbers which melt above the softening temperature of the polymer used and, in spite of this, are sufiiciently soluble in the melted polymer, are particularly valuable.

Clearly, the preferred carriers for the new bis-methylene malonic acid derivatives of formula I are thermoplastic materials which can be made into forms having a large surface at raised temperatures. These are in particular the polyolefines, i.e. polyethylene and the isotactic polymers derived from u-olefines, especially from alkenes having 3 to 6 carbon atoms. In addition the carriers which are distinguished by particularly slight self-colour such as polymers of esters of acrylic and methacrylic acid and polystyrene are important. A third type of carriers in which the bis-methylene malonic acid derivatives according to the invention lead to particularly good results are polymers into which heavy metal salts are incorporated as additional stabilisers or as pigments. These are mainly polymeric halogen vinyl and vinylidene compounds preferably in the form of thermoset compositions such as hard or plasticised PVC.

Because of their easy accessibility and compatability to substrates, symmetrical compounds of formula Ia R represents an alkoxy group containing 1 to 21 C atoms and R represents an alkylene group containing 2 to 12 C atoms are preferred and of these, compounds in which all (R )S and (R )s together contain at least 12, preferably 20to 86, optimally 20 to 48 carbon atoms are'particularly suitable as UV absorbers for polyolefines such as polyethylene, isotactic polypropylene and isotactic poly-4-methylpentene-(l). Of the compounds of formula Ia, the esters having the same number of carbon atoms are distinguished by better compatibility. On the other hand, the amides are preferred for those purposes where particular stability to extraction is required. In this class, often the high melting compounds are preferred as they can be better mixed with, in particular, the pulverulent a-olefine polymers, than low melting or even liquid additives and thus better homogeneity of the finished products is guaranteed.

The compounds of formula Ia are distinguished by high absorption at short wave lengths whilst similar compounds of formula I wherein R or R is not hydrogen have weaker absorption but absorb at longer wave lengths. The good light fastness of compounds of formula la is all the more surprising since analogous cyanoacetic acid ester compounds wherein one of the radicals COR is replaced by the radical CN have very inferior fastness to light.

13v Compounds of formula; (1b) are distinguished principallx, forgtli eir,light fastness in ,oxidisable substrates:

1 have the meanings given in formula Ia, and --,R i'--represents" phenyl, methylphenyl, chlorophenyl or,

: alkoxyphenyl, preferably lower alkoxy-phenyl.

"have a slight tendency to autoxidation, e.g. polyvinyl chlo- 'ride, often even simple phenols are sulficient such as 2,2- IYbis-(4-hydroxyphenyl)-propane. In substrates which are highly subject to autoxidation such as a-polyolefines which, in addition to polyethylene, embrace particularly 'the isotactic types'derived from alkenes having more than [carbon atoms, as well as in the homoand copolymers of butadiene and/or isoprene, sterically hindered phenols have to be used as antioxidants. As examples of the most simple representatives of this class can be mentioned: 2,4- dimethyl-G-tert. butyl phenol, 2,6-di-tert.butyl-4-methyl phenol, 2-tert.butyl.-5-methylphenol and 2,6-di-tert.butyl- 4-rnethoxy phenol. More ditficulty volatile and, therefore, preferred aremononuclear phenols substituted in the side chains such as the alkanol esters of 2,6-di-tert.butyl-4-(2- carboxyethyll-phenol, of 3,S-di-tert.butyl-4-hydroxybenzyl phosphonic acid, 2,6-di-tert. butyl-4-dimethylaminomethyl phenol or phenols containing complex hydrocarbon substituents' such as reaction products of phenol, pcresol, m-cresol with terpenes. Diflicultly volatile and, therefore, suitable, are also the polynuclear phenolic antioxidants such as 4,4'-dihydroxy-2,2 -dimethyl-5,5-di-tert. butyldiphenyl sulphide, 2,2'-dihydroxy-3,3'-di-tert.' butyl-5,5'-dimethyldipheny1 methane, 4-methyl-, 4-ethyl-, 4-tert, butyl-, 4-octyl-, 2,6-bis(2-hydroxy-S-tert. butyl5-methylbenzyl)phenol, 1, l-bis- (4-hydroxy-2-methyl-S-tert.butylphenyl) -propane, 1,1, 3-tris- (4-hydroxy-2-methyl-5-tert.butylphenyl) butane, l,3,5-tris (4-hydroxy-3,5-tert.butylphenyl)-2,4, 6-

trimethylbenzene, 2,4,6-tris-(4-hydroxy-3,5-tert.butylphenyl)-phenol,

the triester of trimethylol. propane and the tetraester of pentaerythrite with 3-(4-hydroxy-3,5-di-tert.butylphenyl)- propanoic acid orthe diester of ethylene glycol with 4- hydroxy-3,5-di-tert.butylbenzoic acid, also 2,4-dioctylmercapto-6-(4-hydroxy-3,5-di-tert, butylphenylamino) 1,3 ,5 -triazine,

2-octylmercapto-4,6-(4-hydroxy-3,5-di-tert. butylphenoxy)-1,3,5 triazine, or

2-(2-octylmercapto ethylmercapto)-4,-6-(4-hydroxy- 3,5-di-tert.butylphenoxy)-l,3,5-triazine.

In order to increase the action of these actual antioxidants, particularly when they are used in lower concentration, synergists can also be admixed into the compositions. The esters of thiodipropionic acid, particularly those of the higher fatty alcohols such as lauryl alcohol or octadecyl alcohol have proved to be particularly suitable. In composition of synthetic plastics containing the UV absorbers, the antioxidants mentioned are added in amounts of 0.001 t011 part by weight and the synergists in amounts of 0.01 to 2 parts by weight per parts by weight of plastic.

Tostabilize the color of plastics in a heat treatment,

it is often of advantage to add, in addition to the UV adsorbers, phosphites such as triphenylphosphite in amounts of 0.01 to 5 parts by weight per 100 parts by weight of plastic. This addition of phosphite can naturally also be supplemented by the admixture thereto of antioxidant and/ or synergist if the substrate, in addition to heat and light sensitivity, is also subject to autoxidation.

Textile materials which can be protected against deteriorating influence of the ultra-violet portion of light by incorporating thereinto or application thereto of bis-methylene malonic acid compounds of Formula I, are crude or processed fibers such as yarns, threads or fabrics, of vegetable, animal or synthetic origin, for instance, cellulose-containing materials such as cotton, jute or sisal on the one hand, and viscose on the other hand, moreover, polyamide fibers such as wool or silk and synthetic superpolyamide fibers such as nylon 6-6 and nylon 6; furthermore, acrylic and vinylic fibers, especially copolymeric, acrylic fibers of improved dyeing properties, fibers from polyvinyl alcohol and modifications of such fibers having improved fastness to wet media; also fibers of vinyl chloride polymers and copolymers; polyester fibers being cellulose derivatives such as cellulose acetate or cellulose propionate or super-polyester fibers, for instance poly- (ethylene glycol terephthalate) and the like fibers of glycols and organic carboxylic acids; finally, polyurethane and polycarbonate fibers can thus be protected.

Application of the compounds falling under Formula I which are to absorb fiber-deteriorating ultra-violet radiation, comprises coating of the surface of the fiber with the light-protecting agent on the one hand, and a homogeneous distribution of the light protecting agent throughout the fiber, penetration of the agent into the fiber being effected on the spun fiber. More in detail, this can be achieved by introducing the fibrous material into a liquor which contains the ultra-violet radiation-absorbing bismethylene malonic acid compound of Formula I either in a dissolved or a finely dispersed state. Solvents or dispersion media for the last-mentioned compounds are, for instance, acetone, methylethyl ketone, methanol, ethanol, ethyl acetate, cyclohexanol, tetrahydronaphthalene, and preferably water. Dispersing agents that may be used in this liquor are suitable products conventional in the textile industry, such as soaps, alkyl and aryl sulfonates and polyethylene glycol condensation products. The textile material is left for a conventional period, ranging from about 20 minutes to 20 hours, in the liquor which can be held at a temperature ranging from about 18 to C., the material being moved in the liquor if necessary. At the end of the treatment, the goods are removed from the liquor, washed if necessary, and dried at room temperature, drying being accelerated if necessary by applymg a vacuum.

It is also possible to spray a solution or suspension of the ultra-violet radiation-absorbing compound, prepared with the above-mentioned solvents or dispersing agents,

onto the textile materials to be protected against the detrimental efiects of ultra-violet light, and then to dry the goods.

The amount of ultra-violet radiation-absorbing compound to be applied to the fibers depends on the type of textile material to be protected and on the degree of protection desired. Generally, an amount of 0.001 to 5%, and

15 preferably of 0.1 to 4%, calculated on the Weight of the fibers is satisfactory.

The following uon-lirnitative examples illustrate the invention further. The temperatures are given therein in degrees Centigrade. Percentages are given by weight unis suitable as alight-stable UV absorber whilst t he closely related comparative substance A is very sensitive photolytically and is thus unsuitable as UV absorber.

Production method A 5 less expressly stated otherwise.

To produce UV absorber No.1, 0.1 mol (29.8 g.) EXAMPLE 1 of 1,4-bis-(p-formyl-phenoxy)-butane (M.P. 103; J. Org. Chem. 26, 475 (1961)), 0.2 mol (32.0 g.) of malonic A solution of 15 g. of acetyl cellulose having on the acid diethyl ester, 0.5 g. of benzoic acid, 2 g. of piperidi ne average 2.5 acetoxy groups per glucose unit, and 0.3 and 100 ml. of benzene are heated for '14 hours"in"'a g. of one of the additives given in the following Table water separator. About 3 ml. of water are distilled off. I, 2.0 g. of dibutyl phthalate and 82.7 g. of acetone is The cooled solution is filtered and the filtrate is concenmade into a film by painting onto a glass plate. After trated. On triturating the honey-like residue, itcrystallises. evaporation of the acetone, cellulose acetate foils are The crude product so obtained ,is first recrystallised obtained which are dried first at room temperature and from methanol and then from ligroin. It melts at,102 then in the oven at 60. Samples of these 0.04 mm. 103 and hasamaximurn UV absorption at about317'nin. thick foils are exposed in a fadeometer and tested from The comparative substance A is produced analogously time to time for the content of UV absorber and for by reacting the bis-formyl compound mentioned which their brittleness. The results obtained are given in Table I. cyanoacetic acid ethyl ester instead of malonic aciddi- TABLE I ethyl ester. It melts at 200. I

Other results obtained with substances according to 3 gfgggf ggg; the invention are given in Table Ia. All UV absorbers Cpd. posure tive still foilson given so protect acetyl cellulose that sheets thereof can Addtwe (hrs') present foldmg still be folded after 500 hours exposure. p 1,4-bis-[4-(2,2-dicarb- 1 24 100 Fold- A light-protection agent of Formula I, in which the g 'i ifggf fgg gi 100 99 $3? groups R are diiferent pairs of ester groups is, for exam- 500 90 Do. ple, 1-[4-(2,2-d1carbobutoxy-ethenyl)-phenoxy]-4-[4:(2, 1,4 biS [4 (2 24 20 Z-dicarbohexoxy-ethenyl)-phenoxy]-butane which is procarbethoxgethenyng8 g lp 3O duced as follows: 0.1 mol (29.8 g.) of 1,4-b1s-(p-formyln a phenoxy)-butane, 0.1 mol (21.6 g.) of dibutylmalonate 24 F 1d and 0.1 mol (27.2 g.) of dihexyl malonate ar'emixed 1 3, with 0.5 g. of benzoic acid and 2 g. of piperidi e 11,1 0 2% u ml. of benzene and refluxed in a water'jseparator'for n 12 hours. The reaction mixture is cooled and filtered and the filtrate is evaporated to dryness. th fg l g seen from Table the addltwe 1 of Chromatographic separation of the oily residue aflords 6 about equal amounts of: I H o1norr,0oo l c=o CHICH,CHICHIO 4 1-[{-(2,2-d1carbobutoxy-etheny1)-phenoxy]-4-[4-(2,2- dicarb ohexoxy-ethenyl) -phenoxy] -butane, CHQCH: 0 O 0 1,4-bis- [4- (2,Z-dicarbobutoxy-ethenyl -phenoxy] -butane /C O O CHaCHa d CH=C\ 1,4-bis-[4-(2,2-dicarbohexoxy-ethenyl)-phenoxy] oooomcrn butane- TABLE Ia Percent of additive (present) Comafter 500 pound Melting hrs. 5 Additive number point, exposure Method a 1,8-bis-[4-(2,2-dicarboethoxy- 2 10a" 85 A ethenyl)-phenoxy]-octane.

b 1,2-bis-[4-(2,2-dicarbobutoxy- 3 v 64 78 A ethenyl)-phenoxy]-ethane.

c 1,Z-bis-[4-(2,2-dlcarbooctoxy- 4 65 A ethenyl)-phenoxy]-ethane.

d 1,2-bis-[4-(2,2-dicarbododecy1oxy- 6 79-80 70 A ethenyl)-phenoxy]-ethane. t

e..- 1,2-bis-[4-(2,2-diearbomethoxy- 6 154 86 A ethenyl)-phenoxy]-ethane.

f 1,8-bis-[4-(2,2-dicarbooetadecyl- 7 78 70 A I oxy-ethenyl)-phenoxy]-octane.

g 1,4-bis-[4-(2,2-dicarboethoxy- 8 111-112 40 B ethenyl)-2-rnethoxy-phenoxy]- butane.

h 1,4-bis-[4-(2,2-diearboethoxy- 9 23 B ethenyl)-3-chloro-phen0xy]- butane.

i 1,4-bis-[4-(2,2-dicarbooctadeeyl- 10 69 546 B.

oxy-ethenyl)-3-methylphenoxy]- butane.

k p-bis-[[4-(2,2-dicarboeth0xy- 11 151-152 80. B

ethenyl)-phenoxy]-methyl]- benzene.

1 1,4-bis-[4-(1-pheny1-2,2-dlcarbo- 12 141 90 C,

ethoxy-ethenyl)-phenoxy]- butane.

m 1,4-bis-[4-(1-pheny1-2,2-diearbo- 13 70 98 D oetoxy-ethenyl)-phenoxy]- butane. v

n 1,S-bis-[-(l-phenyl-Z,2-dicarbo- 14 8 8 C ethoxy-ethenyl)-pl1enoxy]- octane.

o Sebacic-acid-bis-[4-(2,2-dlcarbo- 15 60 E methoxy-etheuyD-anilide].

TABLE Ia-Continued Percent of additive i 1 (present) Comafter 500 pound Melting hrs. Additive 1 number puint, exposure, Method p; l',B-bis[4-(2,2-di5butylamino- 16 A carbonil-ethenyl)-phenoxy1-octane. q- 1,si-bis-[4-(2,2-di-butylaminol7 A 'earbonilethenyl)-phenoxy]-butane. r .1Sebacic-aeid-bis-[4-(2,2-dibutyl- 18 A aminocarhonyl-ethenyl)- s p-bis-{[4-(2,2-di-buty1amino 19 A p carbonyl-ethenyl)-phenoxyl methyll-benzene.

1,8 bis-[4 -(2,2-bis-dibutyl-amino: 20 A carbcnyl-ethenyl)-phenoxy]- i 061181165 I I i u--- 1,4-bis [4=(2,2-di-piperidino-- 21 A "Compounds-2- 7 are' also produced according to the abovemetho'd'A Q Production method B 1 Compounds 8-11 are produced by this method. The synthesis ofexample 9 is given as an example:

(a) 4-(2,2sdicarboethoxy-ethenyl)-3-chlorophenol: 0.1 mol (115.7 g. -of'4-hydroxy-3-chlorobenzaldehyde, 0.1 mol (16.0 g.) of' malonic acid diethyl ester, 3 ml. of piperidine, 0.8igs-of. benzoic acid and 200 ml. of benzene are boiled for10. hours ini aWater separator. The benzene solution is evaporated'to dryness. When recrystallised from toluene,.the residue obtained melts at 114.

. (b)." 1,4:- bis-{442,2 di'carboethoxy-ethenyl)-3-chlorophenoxyJ-butane: 0.05 mol (14.7- g.) of the compound produced under (a) are dissolved in 100 m1. of cold dimethyl formaniide. 0.05 mol (2.7. g.) of dry sodium methylate and a pinclr ot sodium iodide are added to this solution. The solution isthen heated to 5060 and 0.025 mol (5.4 g.) of 1,4-dibromobutane are added Within minutes. The reaction mixture is then refluxed for 45 minutes. After cooling the reaction mixture; it is poured into 300 ml. of water, the precipitate formed is filtered off under suction, washed with water and recrystallised, first from ethanol and" then from ligroin. The compound 9 so obtained melts at 105.

In the production of compound 11, N-methyl pyrrolidone is used as solvent instead of dimethyl formamide.

Production method C Compounds -12 and" 14 are produced by this method which is described below for compound 12:

(a) ,1,4 bis [4 (phenyldichloromethyl) phenoxy]- butane: 0.08 mol (36.0 g.) of 1,4-bis-(4-benzoylphenoxy)- butane and 0.16 mol (33.3 g.) of phosphorus pentachloride are heatedfor 30 minutes at 150. The phosphorus oxychloride formed is then distilled, off from the reaction mixture in vacuo and the residue is taken up in 200 ml. of hot carbon tetrachloride. When cold, the above compound crystallises outof the carbon tetrachloride extract. It melts at 114118 with decomposition.

(b) 1,4 bis [4-(1-phenyl-2,Z-dicarbOethoxy-ethenyl)- phCDQXH-butane: 2.5 g. of pulverised magnesium filings which have been'defatted' with "carbon tetrachloride are covered with half of a mixture obtained from 0.1 mo1 (16.0g.).ofmalonic-acid diethyl esterand 17.5 ml. of abs.

ethanol. The reaction is startedbythe addition of 0.5 ml.

of,.;car b0n tetrachloride. The. reaction mixture is then brought to. reflux temperature by' the gradual addition of the ,other half of the 'malonic ester/ethanol mixture,- and is then refluxedfor 3 hours, 'afterwhich excess alcohol is evaporatedofirin vacuo and a "solution of 0.05 11101 (28.0 .g.) :of the compoundproduce'd under (a) above in 100.;ml...ofdry xyleneis added tothe 50 warm residue. Whehtthe exothermicre'action-has subsided, the mixture iswh'eated for another 2 hours at 120", then cooled and 200 ml. of 10% sulphuric acid are added. The xylene phase is separated from the aqueous phase, washed neutral with water, dried over sodium sulphate and concentrated. Recrystallised from ethanol and toluene, the above compound melts at 141.

Production method D Production method E Compound 15 is produced by this method as follows:

(a) Sebacic acid-bis-(4-formyl-anilide): 0.2 mol (24.2 g.) of p-aminobenzaldehyde (produced from p-nitrotoluene according to Org. Synth. 31, 6' (1951)) are dissolved in 100 ml. of pyridine. 0.1 mol (23.9 g.) of sebacic acid dichloride are added to this solution dropwise While cooling. The reaction mixture is stirred for 1 hour at room temperature, heated for 5 minutes at cooled and then 200 ml. of water are added. The precipitate formed is filtered 01f, washed with water and recrystallised from ethanol and then from glacial acetic acid. The compound so obtained melts at 138-440.

(b) Sebacic acid-bis-[4 (2,2 dicarboethoxy-ethenyl)- anilide]: 0.025 mol 10.2 g.) of sebacic acid-bis-(4-formylanilide), 0.05 mol (6.6 g.) of malonic acid dimethyl ester, 1 g. of piperidine and 0.2 g. of benzoic acid in ml. of benzene are boiled for 12 hours in a water separator. The reaction solution is cooled whereupon the compound crystallises out in the form of pale yellow needles. On recrystallising from methylethyl ketone, these melt at 185.

EXAMPLE 2 0.5 by weight of an additive given in Table II are added to 'difficultly combustible liquid polyester resin and the mixture together with 1% by weightof benzoyl peroxide is polymerised at 80 into 2.5 mmpthick plates. The plates are subsequentlycured at Q I After-exposure, plates so produced turn considerably less' b'rown'than plates produced withoutthe additives above mentioned When they are exposed under the same conditions. I f The polyester resin used is produced as follows: Amixture of 343 g. of maleic acid anhydride and 428 g. of tetra: chlorophthalic acid anhydride is added in portions to an 80 hot mixture of 170 g of ethylene glycol and 292 g. of diethylene glycol. Afterreplacing theair in the reaction vessel'by nitrogen, the' ternpera ture is raisedto within 1 hour, then to210 within 9.h ours. and so maintained for 19 1 hour. The mass is then cooled to 180, a vacuum pump is connected and the pressure is slowly reduced to 100 Torr. These conditions are maintained until the acid number of the reaction mixture has fallen below 50.

100 g. of the polyester so obtained are mixed with 50 g. of styrene and the mixture is polymerised under the conditions described above.

Similar results are obtained if, instead of tetrachlorophthalic acid, the equivalent amount of phthalic acid anhydrideis used. The resultant polyester resin in this case however is not diflicultly combustible.

If in the procedure described above, the styrene is replaced by methylmethacrylate, then plates are obtained which in themselves tend to turn brown less and, in addition, can be more easily stabilised.

methoxyphenoxy1-oetane.

Compound No. 22 is produced as follows by the method B:

(a) Production of the malonic acid dioctadecyl ester: 0.54 mol (56.9 g.) of malonic acid, 1.1 mol (297 g.) of stearyl alcohol and 500* ml. of benzene are boiled for 20 hours in a water separator and then, in all, 15 g. of ptoluene sulphonic acid are added in portions every two hours. 20 ml. of water are separated. The benzene solution obtained is cooled with ice and the ester which separates is filtered 01f under suction. On recrystallising from acetone, 77% of the theoretical amount of pure malonic acid dioctadecyl ester is obtained (M.P. 60).

(b) Production of p-(2,2 dicarbooctadecyloxy-ethenyl)-phenol: 0.2 mol (24.5 g.) of p-hydroxybenzaldehyde, 0.2 mol (121.5 g.) of malonic acid dioctadecyl ester, 5 ml. of piperidine, 1 g. of benzoic acid and 300* ml. of benzene are boiled for 12 hours in a water separator. 8.5 ml. of water are removed. The benzene solution ob tained is concentrated in vacuo. The residue is recrystallised from acetone and then melts at 69.

Production of 1,4-bis-[4-(2,2-dicarbooctadecyloxyethenyl)-phenoxy]-butane: 0.06 mol (42.7 g.) of the above phenol, 0.06 mol (3.24 g.) of anhydrous sodium methylate and a pinch of sodium iodide are added one after the other to 100 ml. of cold dimethyl formamide. The mixture is heated to 5060 and 0.03 mol (6.5 g.) of dibromobutane are added within minutes. On completion of the addition, the reaction mixture is refluxed for 45 minutes, then cooled with ice, and acetone is added dropwise while stirring until the precipitate, which at first was amorphous, crystallises. The crude 1,4-bis-[4-(2,2-dicarbooctadecyloxy-ethenyl)-phenoxy]-butane is filtered off under suction and recrystallised from methylethyl ketone. In this way 19 g. of pure product are obtained. M.P. 82 (not sharp).

The compounds Nos. 23-27 are obtained analogously by the method B, the corresponding malonic acid derivatives being used as starting materials. When producing malonic acid di-(fl-hydroxyethyl)-ester, the use of a great excess of ethylene glycol is recommended.

Compound No. 2 is produced as follows by the method B:

(a) 0.5 mol (61 g.) of p-hydroxybenzaldehyde, 0.5 mol g.) of malonic acid diethyl ester, 4 ml. of piperidine and 1 g. of benzoic acid are boiled in 500 ml. of benzene for 14 hours in a water separator. 8.6 ml. of water are separated. The benzene solution obtained is filtered and concentrated. The residue becomes solid on rubbing with a little ethanol. The p-hydroxybenzylidene malonic acid diethyl ester is recrystallised from ethanol and melts at 93. Yield about 56%. v

(b) 0.1 mol (26.4 g.) of p-hydroxybenzylidene malonic acid diethyl ester, then 0.1 mol (27.2 g.) of 1,8-dibromooctane and a pinch of potassium iodide are added one after the other to a cold ethylate solution prepared from 2.3 g. of sodium metal and 200 ml. of ethanol. The orange red solution obtained is refluxed for 14 hours whereupon its colour slowly changes to yellow-orange. After removal of the ethanol and rubbing the residue, a crystalline mass is obtained from which, by washing with water and recrystallisin'g from ethanol, 1,8-bis-[4-(2,2-dicarboethoxy-ethenyl)-phenoxy]-octane is obtained, M.P. 102- 103". There is a great depression of the melting point when it is mixed with compound 1 of example 1 which, by chance, has a similarly high melting point.

The compounds Nos. 28-30 are produced analogously to compound No. 2 by the method B. Instead of p-hydroxybenzaldehyde, an equivalent amount of 4-hydroxy- 3-chlorobenzaldehyde, 4-hydroxy-3-methyl benzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively is used.

Compound No. 24 is produced by the method A. It crystallises with 1 /2 mol of water. It begins to melt at EXAMPLE 3 parts of methacrylic acid methyl ester, 0.5 part of an additive given in Table III and 0.2 part of lauroyl peroxide are mixed and the mixture is polymerised at a temperature of 50-70 into sheets of 2 mm. thickness.

As can be seen from the following Table, such sheets can be used as colourless UV filters.

TABLE III Percent transmission of light of wavelength 340 430 nm. nm.

Compound Additive number a p-Bis-[[4-(2,2-dicar boethoxy-ethenyD- phenoxy]-methyl]- benzene.

b 1,4-bis-[[4-(2,2-dicarboethoxy-ethenyD- phenoxy]-methyl]- eyclo-hexane (mixture of cis and trans).

e 1,4-bis-[4-(2,2-dicar- 1 ,1

boethoxy-ethenyD- phenoxy1-butane.

d 1,12-bis-[4(2,2-dicarboethoxy-ethenyD- phenoxy]-dodecane.

e 1,8-bis[4-(2,2-dicarboethoxy-ethenyD- phenoxy]-3,6-dithiaoctane.

i None Method while stirring well, the pale yellow crystals of crude'p bis-[[4 (2,2. dicarboethoxy-ethyl)-phenoxy]-methyl]- benzene which precipitate are filtered 01f under suction, washed with water and recrystallised from ethanol and EXAMPLE 4 A mixture of 600 g. of pulverulent emulsion polyvinyl chloride (K value 72, bulk density 0.43), 330 g. of dioctyl phthalate and 10 g. of an additive given in Table IV are worked up into foils on a set of two mixing rollers at 150.

On exposing foils so produced, brown spots only appear after 1.5 to 2 times longer time than they appear on similar foils produced without the addition of the substances of Table IV.

Similar results are obtained if polyvinyl chloride having a K value of 74 and bulk density of 0.46 is used.

The addition of 10 g. of barium-cadmium laurate to the mixture mentioned in the first paragraph of this example produces foils which are stabilised to the effects of heat and light also.

ethenyl)-diphenyloxide.

To produce the UV absorber No. 34 by the method A 0.1 mol (29.8 g.) of 1,4-bis-p-forrnyl-phenoxy-butane, 0.2 mol (31.6 g.) of malonic acid bis-ethylamide, 0.5 g. of benzoic acid, 2 g. of piperidine and 200 ml. of benzene are boiled for 14 hours in a water separator. (The malonic acid bis-ethylamide is obtained by reacting malonic acid ethyl ester with ethylamine, M.P. 148.) From the cooled solution the 1,4-bis-[4-(2,2-bis-ethyl-aminocarbonylethenyl)-phenoxy]-butane is filtered off and recrystallised from chlorobenzene (M.P. 214).

The compounds Nos. 35-39 are produced in a corresponding way by reacting equimolar amounts of p,p'-bisformyl-diphenyl ether (M.P. 55, CA 59, 11465 e), 1,2- bis-p-formyl-phenoxy-ethane (M.P. 123, J. Org. Chem. 26, 475 (1961)) instead of the 1,4-bis-p-formylphenoxy butane used with the corresponding amounts of malonic acid esters in an analogous way.

EXAMPLE 5 Polyethylene of medium molecular weight 28,000 and a density of 0.917 is mixed at 180 in a Brabender plastographwith 1% of its total weight of an additive of Table V and 0.5% of 4-(2-carbooctadecyloxyethyl)-2,6- ditert.butyl phenol. The mass obtained is then pressed in a plate press at 165 into 1 mm. thick plates.

On weathering, these plates have considerably less tendency to brittleness than those without the addition of the additives mentioned. 7

Similar results are obtained if, instead of the polyethylene, polypropylene is used; this must then be mixed at 220 and pressed at 180. If instead of 4-(2-carbooctadecyloxyethyl) 2,6-di-tert.butyl phenol, 0.5% of 4-hydroxy 3,S-di-tert.butyl-benZyl-di-tert.octadecyl phosphonate is used, then with otherwise the same procedure as given above, similar results are obtained. v

TABLE V Compound Additive number Method 2. 1,4-bis-[4-(2,2-dicarbotetra-decyloxw" 23 B ethenyl)-phenoxy]-butane. b 1,4-bis-[4-(2,Z-dicarbooeta-deeyloxy- 22 B ethenyl)-phenoxy1-butane. e 1,6-bis-[4-(2,2-dicarboocta-declyoxy- 42 B ethenyl)-phenoxy]-hexane.

The compound No. 23 is produced as follows by the method B: 0.1 mol (5.4 g.) of sodium methylate and a pinch of potassium iodide are added to 0.1 mol (60 g.) of p-(2,2 dicarbotetradecyloxy-ethenyl)-phenol [produced analogously to example 2b), M.P. 49-50] in 200 ml. of dimethyl sulphoxide and 0.05 mol (10.8 g.) of dibromobutane are added dropwise to the solution obtained at 50, the addition being made within 1 hour. After stirring for 8 hours at 40-50, the dimethyl sulphoxide is evaporated otf in vacuo. The residue is taken up in acetone, precipitated sodium bromide is filtered off from the hot solution, the filtrate is cooled and the precipitated 1,4-bis-[4- (2,2 dicarbotetradecyloxy-ethenyl)-phenoxy]-butane is recrystallised from hexane. It melts at The compound No. 42 is obtained if, instead of p-(2,2 dicarbotetradecyloxy-ethenyl)-phenol, 0.1 mol (72 g.) of the p-(2,2-di-carbooctadecyloxy-ethenyl)-phen0l described under 2b) is condensed in an analogous way with 0.05 mol (12.2 g.) of 1,6-dibromohexane.

EXAMPLE 6 Polypropylene of medium molecular weight 60,000 and a density of 0.96 is mixed at 220 in a Brabender plastograph with 1% of its total Weight of an additive of Table VI, 0.2% of bis-(4-hydroxy-2-methyl-5-tert.butyl)-phenyl sulphide, 0.2% of dilauryl thiodipropionic acid and 0.2% of tri-octadecyl phosphite. The mass so obtained is pressed in a plate press at 180 into 1 mm. thick plates.

On weathering, the plates so obtained have a considerably less tendency to brittleness than those without the addition of the additive of Table VI mentioned.

Similar results are obtained if, instead of the bis-(4-hydroxy 2-methyl-5 tert.butylphenyl)-sulphide, 1,1,3-tris- (4-hydroxy-5-tert.butyl-Z-methyl-phenyl)-butane is used.

TABLE VI Compound Additive number Method a. 1,2-bis-[4-(2,Z-dicarbooctadecyloxy- 43 B ethenyl)-phen0xy]-ethane. b p-bis-[[4-(2,2-dicaIbooetadecyloxy-- 44 B ethenyl)-phenoxy]-methyl]-benzene. c 1,8-bis-[4-(2,2-dicarbohexadecyloxy- 45 B ethenyl)-phenoxy]-3,6-dithlaoctane.

Compound No. 43 is produced by condensing 0.02 mol (14.4 g.) of the phenol produced according to example 2b) with 0.01 mol (1.9 g.) of ethylene bromide in 30 ml. of dimethyl forrnamide in the presence of 1.1 g. of sodium methylate and a pinch of sodium iodide according to method B. The solvent is evaporated to dryness invacuo and the residue is recrystallised twice from hexane. The compound No. 43 melts at 73 EXAMPLE 7 Similar results'are obtained if, instead of 0.1% of tritert.butyl phenol, 0.1% of 2,6-di-tert.butyl4-(carbooctadecyloxyethyl)-phenol are used.

TABLE VII Com- Additive pound a 1,4-bis-[4-(2,2-dicarboethoxy ethenyl)-phenoxy]- 1 butane. b 1,Z-lfls-M-(2,2-diearboethoxy-ethenyl)pl1enoxy]- 3!;

et ane. p-Bis-[[4-(2,2-dicarboethoxy-othonyl)-phenoxy]- ll methyll-benzone. d 1,8-bis-[4-(2,Z-dicarboethoxycthonyl)-phenoxy]- 2 octane.

EXAMPLE 8 Bleached maple veneer is painted with a lacquer for wood of the following composition:

15.0 parts by weight of cellulose acetate Cellit F 900 (Bayer Leverkusen, Germany, having about 56% acetic acid content),

10.0 parts by weight of dimethyl glycol phthalate,

2.25 parts by weight of compound No. 11 p-bis-[4-(2,2- dicarboethoxyethenyl) -phenoxy] -methyl] -benzene (corresponding to 15% by weight, calculated on the cellulose acetate),

5.0 parts by weight of methyl alcohol,

10.0 parts by weight of toluene and 50.0 parts by weight of ethyl acetate.

The natural yellowing of the wood is retarded by this lacquer.

EXAMPLE 9 Bleached maple veneer is painted with a lacquer of the following composition:

16.0 parts by weight of Acronal 4 F (BASF) [poly-(butylacrylate) 16.0 parts by weight of nitrocellulose E 620, 35% butanol moist (medium viscosity) 2.25 parts by weight of compound No. 35, p,p'-bis-(2,2-

dicarboethoxy-ethenyl)-diphenyl oxide,

44.0 parts by weight of butyl acetate, and

24.0 parts by weight of toluene.

The natural yellowing of the wood is retarded by this lacquer. Similar good results are obtained on using 1,2- bis-[4-(1 phenyl-Z-cyano 2 carbomethoxy-ethenyD- phenoxy]-ethane (compound No. 46) instead of compound 21.

EXAMPLE 10 EXAMPLE 11 One part of 1,4-bis-{4-[2,2-di-2-methoxy-ethoxycarbonyl)-ethenyl]-phenoxy}-butane is dissolved in 50 parts of acetone and the resulting solution is added with good stirring to a 40-Warm mixture of 5000 parts of water' and parts of tetradecyl-heptaethylene-glycol ether.

100 parts of nylon 66 yarn are introduced into this liquor and the temperature of the latter is raised to 95 within 30 minutes. After the yarn has been treated at a temperature of 95 to 100 for about 30 minutes it is .withdrawn from the liquor, rinsed with water and dried.

Compared with non-treated nylon 66, the resulting treated yarn shows increased light resistance.

We claim:

' 1. A'compound of-theformula 2. A compound as defined in claim 1, which is of the formula CzHsOOC 3. A compound a defined in claim 1, which is of the formula 00 OCuHzg C O OCHHQB 4. A compound as defined in claim 1, which is of the formula CZH5OOC\ I C=CH@O(CH2)BO o o0o2m 0 -CH=C\ COOCzHs 5. A compound as defined in claim 1, which is of the formula CBHUOOC CsHnO O C 6. A compound as defined in claim 1, which is of the formula References Cited UNITED STATES PATENTS 12/1970 Kirchmayr et al. 260465 D OTHER REFERENCES Phillips, J. Am. Chem. Soc., vol. 70, pp. 452454 (1948).

Chemical Abstracts, vol. 67, p. 2162 (abstract no.

22,492x), 1967 (abstract of Netherlands Appl. 6,610,370).

JOHN D. RANDOLPH, Primary Examiner 

